The present invention relates to a sustained-release aromatic comprising a gradually releasable perfume derivative. The present invention particularly relates to a sustained-release aromatic comprising a gradually releasable perfume derivative which is decomposed by micro-organisms to release an aroma component, and to a method for the detection of micro-organisms by the sustained-release aromatic.
Various methods has been used in the prior art to blend perfumes in a sustained-release aromatic composition, such as cosmetics, e.g. hair liquids, hair mousses and antiperspirant agents, room aromatics and drinks and foods. For example, in liquid products use have been made of water-solublilized perfumes obtained by dissolving oily perfumes in a solvent or carrier such as alcohols, propylene glycol, carbitol, etc. Alternatively, oily perfumes have been solubilized or emulsified in liquid or creamy products by the use of a surfactant. In powdery or solid products, these oily perfumes has generally been blended as powder or granule made by means of adsorption, capsulation or coating with the aid of a proper excipient, or as a clathrate compound.
Perfumes added to a sustained-release aromatic composition in the prior art have a problem that they start to be released immediately after applied to, for example, a human body and is quickly lost with the passage of time. In order to prevent such too quick diffusion of aroma, carriers are added. However, this method was insufficient in the effect. The perfumes added as a clathrate compound or a capsulated material are excellent in keeping the perfumes, but not too much excellent to emit aroma. Accordingly, they are not always satisfactory as a perfume-carrying material. Thus, there has been a strong desire for a sustained-release aromatic composition which stably generates aroma to a proper extent over a long time.
In order to solve this problem, there has been proposed an aromatic composition comprising an enzyme or acid and a derivative of a perfume which decomposes by the action of the enzyme or acid to form a perfume (e.g. glycosides or glycerides of a perfume, or amino acid or peptide derivatives of a perfume) (Japanese Patent Application Laid-Open Nos. Hei-4-170961/92, Hei-5-230496/93 and Hei-5-239491193). However, in the aromatic composition comprising an acid, it is necessary to blend the acid at a high concentration in the composition. This, therefore, causes a problem of safety when it is put on the skin.
There has also been proposed an oral composition in which at least one glycoside selected from thymol glycosides, cis-3-hexenol glycosides and methyl salicylate glycosides is added (Japanese Patent Application Laid-Open No. Hei-3-90016/91). When the composition is used, the glycoside is hydrolyzed by the action of glucosidase in saliva to release thymol, cis-3-hexenol or methyl salicylate, respectively, and exhibit flavor.
In addition to the aforesaid glycosides, there are known glycosides of mono-terpenes, such as perillyl alcohol, which are present in natural plants and can be synthesized easily and which exhibit pharmacological activity in cooperation with other components (Japanese Patent Application Laid-Open Nos. Hei-3-287597/91 and Hei-4-300889/92). However, the aforesaid publications do not refer to its aromatic effect.
An agent which gradually releases active components has also been proposed. This is an ester of a polyvalent alcohol having a carboxylic group or an oxyalkylene derivative of a polycarboxylic acid with a hydroxide group-containing active component (Japanese Patent Application Laid-Open No. Hei-3-17025/91). However, because the molecular weight of the polyvalent alcohol or the oxyalkylene derivative is relatively high, a ratio of aromatic components contained as the active component is small. Accordingly, it is unsatisfactory in an extent of aroma. In addition, as the aforesaid agent generates the active components as a result of hydrolysis, it is poor in stability during storage for a long period. This leads to a problem that aroma decreases with the passage of time.
A purpose of the present invention is to provide a sustained-release aromatic which is excellent in keeping aroma and a method for the detection of micro-organism using the same.
The present inventors have made researches to provide a sustained-release aromatic which stably generates aroma to a proper extent over a long time. As a result, we have found that when a perfume derivative selected from glycosides, phosphate ester derivatives, amino acid derivatives and carboxylic acid derivatives of perfume components is put on the skin, the perfume derivative itself releases very weak aroma, but it is decomposed by bacteria usually present on the skin to generate perfume components and the gradual decomposition by bacteria provides stable release of aroma over a long time. It has further been found that it does not happen that aroma decreases quickly with the passage of time by increased decomposition of the perfume derivative with propagation of these bacteria usually present on the skin which are safe for organisms. In addition, it has been found that as yeast also gradually decomposes the aforesaid perfume derivative, aroma is released stably over a long time.
The perfume derivatives contained in the sustained-release aromatic of the invention have no aroma or extremely weak aroma in themselves. Accordingly, it is possible to detect the presence and propagation of micro-organism such as bacteria usually present on the skin or yeast using the sustained-release aromatic of the invention by detecting the released aroma.
The present invention provides a sustained-release aromatic, characterized in that the aromatic comprises at least one perfume derivative as an active component selected from glycosides of perfumes, phosphoric acid ester derivatives of perfumes, amino acid derivatives of perfumes and carboxylic acid derivatives of perfumes, and contains no enzyme or acid which decomposes the perfume derivative, wherein the perfume derivative is decomposed by bacteria usually present on the skin or yeast to release a perfume component to exhibit aroma.
The present invention also provides a method for the detection of micro-organisms, characterized by use of a sustained-release aromatic comprising at least one perfume derivative as an active component selected from glycosides of perfumes, phosphoric acid ester derivatives of perfumes, amino acid derivatives of perfumes and carboxylic acid derivatives of perfumes, wherein the perfume derivative is decomposed by a micro-organism to diffuse aroma which is then detected.
The sustained-release aromatic of the present invention comprises a perfume derivative which is not volatile, or less volatile, compared to a perfume, and a volatile perfume is released gradually by the action of micro-organisms only after it is put into use. Accordingly, the perfume derivative is not decomposed during storage before it is used and, therefore, is excellent in a long time stability. The sustained-release aromatic of the present invention does not contain any enzyme nor acid which decomposes the aforesaid perfume derivative to release the perfume.
Meanwhile, the invention disclosed in Japanese Patent Application Laid-Open No. Hei-4-170961192 provides an aromatic composition which comprises a blended perfume comprising at least each one of top note, middle note and base note which are different from each other in volatility, characterized in that the whole or a partial amount of the at least one perfume is blended, together with an enzyme, in the form of a precursor, e.g. glycosides or glycerides of a perfume, or amino acid or peptide derivatives of a perfume, which converts into the perfume via decomposition by the action of the enzyme. However, in the aromatic composition proposed in the above publication, immediately after the precursor is blended with the enzyme, the precursor decomposes quickly. Accordingly, it has a drawback that aroma becomes weaker with the passage of time. Furthermore, it has another drawback that when the precursor is stored together with the enzyme as a mixture, for instance before it is used or after a partial amount of it is used, the aforesaid precursor is decomposed and, therefore, the composition is poor in a long time stability. In the aforesaid publication, there is proposed an aromatic agent, bathing agent or detergent which separately comprises a principal agent containing the precursor and a sub-agent containing the enzyme. In a working example, there is described a bathing agent comprising the two agents, where aroma was evaluated only for two hours after the two agents were added to warm water in a bath. Duration of the aroma of two hours might be sufficient for a bathing agent, but is insufficient for other applications. In addition, it is inconvenient to separately prepare and store the two agents and to mix them when they are used. In another working example in the above publication, the perfume derivative was placed in a bottle and lifted by a wick little by little to be vaporized through a vaporizing paper. Alternatively, there is described an aromatic in a gel form, where an enzyme is immobilized in an ager gel together with the aforesaid precursor. However, there is a problem that such a manner of application is inconvenient or their usage is restricted. Various procedures are needed to extract and purify enzymes from organisms. Furthermore, enzymes are unstable after taken out of organisms due to change of environment. For example, enzymes are unstable at or above 5xc2x0 C. when they are brought into the form of an aqueous solution. As an enzyme solution is unstable particularly at a low concentration, it is necessary to prepare it at a high concentration. However, at a high concentration, there are problems that the enzymes tend to precipitate and offensive odor occurs or bacteria propagate. Accordingly, their applications are restricted to particular types of formulation such as a powder type agent. Enzymes are also unstable particularly to heat.
Meanwhile, the aromatic according to the invention is stable for a long period because it contains neither enzyme nor acid which decomposes the perfume derivatives. In order to emanate aroma, it is enough to apply this aromatic on a proper place where micro-organism is present and, therefore, the aromatic may take any forms such as liquid, powder, gel or aerosol.
The present invention will be further specifically explained below.
A perfume derivative used in the invention is glycosides of perfumes, or phosphate acid ester derivatives of perfumes, amino acid derivatives of perfumes or carboxylic acid derivatives of perfumes which derivatives are decomposed by micro-organisms to release a perfume component. As the aforesaid perfumes, any known perfumes are satisfactorily used. The aforesaid perfume derivatives may be synthesized in known methods.
A sugar part of the glycosides used in the invention may include monosaccharides such as glucose, galactose, mannnose, rhamnose, xylose, ribose, arabinose, glucosamine and galactosamine; and disaccharides such as lactose, maltose, sucrose, cellobiose, isomaltose and epilactose.
The aglycon corresponding to the perfume component in the aforesaid glycoside may include alcohols such as aliphatic alcohols, for example, pentanol, 3-methyl-butanol, 3-methyl-1-pentanol, 2-hexanol, 2-heptanol, undecanol, cis-3-hexenol, cis-6-nonenol, 2,6-nonadiene-1-ol, 9-decenol, geraniol, linalool, nerol,citronellol, hydroxycitronellol, myrcenol, 3,7-dimethyloctanol, farnesol, nerolidol, and lavandulol; cycloaliphatic alcohols, for example, menthol, terpineol, piperitol, perillyl alcohol, carveol, myrtenol, santalol, cedrol, patchouli alcohol, ionol, and hydroxydamascone; aromatic alcohols, for example, benzyl alcohol, cumic alcohol, 2-phenylethyl alcohol, phenylpropyl alcohol, cinnamic alcohol, and xcex1-amylcinnamic alcohol; phenols such as eugenol, vanillin, anisalcohol, raspberry ketone, vanillyl alcohol, piperonyl alcohol, and sesamol; and thiols such as methyl mercaptane, ethyl mercaptane, isopropyl mercaptane, propyl mercaptane, allyl mercaptane, thiogeraniol, thioterpineol, thiolinalool, thiomenthol.
In this specification, the term xe2x80x9caglyconxe2x80x9d means the whole non-sugar part which is bound to a sugar part via O-glycoside bond or S-glycoside bond. The bond between aglycon and sugar may be either an xcex1- or xcex2-bond. The glycosides used in the invention may be either an xcex1- or xcex2-form, or a mixture of xcex1- and xcex2-forms. xcex2-Form is preferred because it is easily decomposed by micro-organism, particularly bacteria usually present on the skin.
Many of these glycosides are commercially available with ease. They may also be easily synthesized in known methods. For example, they may be easily synthesized by reacting sugars with the aforesaid alcohols or thiols in the presence of acids. It is possible to synthesize only the xcex2-form using the known Koenigs-Knorr Reaction (Chem. ber., 34,957(1901) ). Alternatively, objective glycosides may be purified by, for example, column chromatography.
The phosphoric acid esters of perfumes used in the invention may include phosphates and pyrophosphates. Alkyl moieties corresponding to a perfume component may include alkyl, alkenyl, alkynyl and aralkyl groups having 5 to 15 carbon atoms which may be branched and may have functional groups such as amyl, nonyl, geranyl, neryl, linalyl, hexenyl, nonadienyl, phenethyl and cinnamyl groups. As a perfume component, use may be made of the same ones as mentioned for the aforesaid glycosides, some of which fall also under the definition given here.
Many of these phosphoric acid ester derivatives are commercially available with ease. They may also be easily synthesized in known methods. For example, they may be easily synthesized from alkyl alcohols or alkyl halogenides and phosphorus oxychloride or diphosphoric esters in accordance with the known method described in J. Org. Chem. 1989, 54, 1338-1342; or Methods. Enzymol., 110,130(1985).
The amino acid derivatives of perfumes used in the invention may include amino acid esters, N-alkyl amino acids, S-alkyl amino acids and S-oxide alkyl amino acids. An amino acid of which the amino acid derivative is composed may include cystein, alanine, glutamic acid, glycine and phenylalanine. Alkyl moieties corresponding to a perfume component may include alkyl, alkenyl, alkynyl and aralkyl groups having 5 to 15 carbon atoms which may be branched and may have functional groups such as amyl, nonyl, geranyl, neryl, linalyl, hexenyl, nonadienyl, phenethyl and cinnamyl groups. As a perfume component, use may be made of the same ones as mentioned for the aforesaid glycosides, some of which fall also under the definition given here.
The carboxylic acid derivatives of perfumes may include monocarboxylic acid esters and polycarboxylic acid esters. The monocarboxylic acid ester includes quinic acid, caffeic acid, ascorbic acid and glucuronic acid. As a perfume component, use may be made of the same ones as mentioned for the aforesaid glycosides.
Many of the aforesaid amino acid derivatives and monocarboxylic acid derivatives of perfumes are commercially available with ease. They may also be easily synthesized in known methods. For example, they may be easily synthesized from amino acids or carboxylic acids and alcohols or alkyl halogenides in accordance with a process described in xe2x80x9cSynthesis and Reactions in Organic Chemistry, New Lecture Series of Experimental Chemistry 14xe2x80x9d, edited by The Chemical Society of Japan, Maruzen Ltd.
The polycarboxylic acid derivative used in the invention is an ester of a perfume component and a polycarboxylic acid. The polycarboxylic acid includes succinic acid, tartaric acid and citric acid. The polycarboxylic acid group may be those substituted by an ethyl or other group. As a perfume component, use may be made of the same ones as mentioned for the aforesaid glycosides. The polycarboxylic acid derivative in the present invention may be available with ease. They may also be easily synthesized by reacting a polycarboxylic acid with an alcohol corresponding to the perfume component in the presence of an acid. They may also be synthesized by an ester exchange reaction of a lower alkyl ester such as triethyl citrate with the perfume component. If desired, these polycarboxylic acid derivatives may be used after purified by, for example, distillation or column chromatography.
In the prior art, there have been used citric acid monoalkyl esters or trialkyl esters as an emollient agent in cosmetics or triethyl citrate as a diluent for a perfume. These compounds are undesirable as a polycarboxylic acid derivative of a perfume in the present invention because no consideration is paid to substituent groups for aroma.
The perfume derivatives mentioned above may also be obtained as an extract from a natural resource containing the aforesaid perfume derivatives by a process proposed by the present inventors and described in Japanese Patent Application Laid-Open No. Hei-6-057288/94.
The sustained-release aromatic according to the invention may contain at least one of the perfume derivatives mentioned above.
Many of the perfume derivatives used in the invention are soluble in water and, therefore, may be used as an aqueous solution. When their solubility in water is low, they may be used by being solubilized or emulsified, if needed.
A solubilization method for the aforesaid perfume derivatives may include one in which the perfume derivative is dissolved in mono- or polyvalent alcohols, e.g. ethanol, glycerol, propylene glycol, carbitol, diacetin, triacetin, or sorbit, or with a surfactant such as alkylbenzene sulfonic acid salts, higher alcohol sulfuric acid ester salts, alkyltrimethylammonium chlorides, betaines, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylenepolyoxypropylene block polymers, or sucrose aliphatic acid esters, and is diluted with water if needed.
An emulsification method for the aforesaid perfume derivatives may include one in which the perfume derivative is homogenized by a colloidal mill or a homogenizer together with a proper amount of an emulsifier, an emulsification stabilizer or a surfactant, such as sucrose aliphatic acid esters, aliphatic acid monoglyceride, sorbitan aliphatic acid esters, propyleneglycol aliphatic acid esters, polyoxyethylene sorbitan aliphatic acid esters, gum arabi, tragacanth gum, methyl cellulose, casein, soybean lecithin, yolk lecithin, starch, sodium alginate, locust bean gum, guar gum, carrageenan, sorbit, propylene glycol, glycerol, xanthan gum, pectin, cellulose derivatives, starch derivatives, cyclodextrin, polyglycerol aliphatic acid esters, saponin, or sucrose.
The sustained-release aromatic according to the invention may take any forms, for example, liquid, powder, gel or aerosol.
A proper excipient such as dextrin, starch or processed starch may be added to the dissolved, solubilized or emulsified perfume derivative, and then the mixture may be dried and powdered by, for example, spray drying or vacuum drying to prepare the sustained-release aromatic.
The aforesaid derivative in a dissolved, solubilized, emulsified or powdered form may be mixed with a proper solvent or carrier and then packed in a vessel with carbon dioxide gas, nitrogen gas or freon gas to prepare a sustained-release aromatic in an aerosol form.
A concentration of the perfume derivative in the sustained-release aromatic of the invention may vary depending on various conditions such as a type of the composition used and a threshold value of the perfume which constitutes the aforesaid perfume derivative and, therefore, shall not be restricted to particular one. In general, the concentration of the perfume derivative is preferably about 0.001 to about 20% by weight, more preferably about 0.005 to about 10% by weight. More specifically, it is preferred to add the perfume derivative in a range of about 0.001 to about 5% by weight in hair cosmetics for human body such as a hair liquid, hair cream or hair mousse, and in a range of about 0.001 to about 10% by weight in skin cosmetics such as a an antiperspirant agent, depending on a site of the skin.
The inventors have conducted researches to find combinations between micro-organisms and the perfume derivatives in which the perfume derivative can be gradually decomposed to emit aroma over a long time.
Bacteria usually present on the skin are usually found on, for example, the skin, head skin or hair of human beings or animals, or on the surface of fiber products such as clothes, e.g. under wears or socks. Examples of the bacteria include Staphylococcus epidermidis, Propionibacterium acnes, Coryneform bacteria (aerobic dephtheroids), Staphylococcus aureus, Ptyrococcus sp., and Micrococcus sp.
The present inventors have noted that axillary odor which is a main cause of unpleasant odor on a human body is produced by decomposition of fluid secreted from the apocrine gland with Corynebacterium which is usually present on the axillary fossa, and have searched for perfume derivatives which are decomposed by bacteria such as Coryneform bacteria to emit aroma. As a result, it has been found that it is preferred in the case of Coryneform bacteria to blend a perfume glycoside, preferably one in which a perfume component is bound to sugar in xcex2-bonding, particularly in a sustained-release aromatic for an antiperspirant agent. It has not been known in the prior art that Corynebacterium, which is one of the bacteria usually present on the skin and concerned with axillary odor, stably causes aroma from, for example, a perfume glycoside having xcex2-bonding, which has been found first by the present inventors. In addition, it has also been found first by the present inventors that other bacteria usually present on the skin stably cause aroma from a perfume glycoside.
The aforesaid yeast is not restricted to particular ones. Use may be made of, for example, ones belong to Endomycetales such as Saccharomyces, Hansenula, Kluyveromyces, Lodderomyces, Pichia, Nadsonia, Saccharomycodes, Hanseeniaspora, Schizosaccharomyces, Lipomyces, Endomycopsis and Nematospora; ones belong to Ustilaginales such as Leucosporidium and Rhodosporidium; ones belong to Sporobolomycetaceae such as Bullera, Sporoboromyces and Sporidiobolus, [all of the above are called Ascomycotina yeast]; Brettanomyces, Crytococcus, Kloeckera, Rhodotorula and Sterigmatomyces, which are called non-spore yeast, with Saccharomyces cerevesiae being particularly preferred because of its low cost, availability and easy handling.
As the micro-organism in the present invention, preference is given to bacteria usually present on the skin and yeast. As the aforesaid perfume derivative, preference is given to a perfume glycoside, particularly a glycoside in which a perfume component is bound to sugar in xcex2-bonding.
The sustained-release aromatic according to the invention is used to mask various odors released from, for example, the skin, head skin or hair of human or animal bodies, or to wear pleasant aroma actively. It""s applications are not restricted to particular ones. Examples of the present aromatic used for human body may include hair cosmetics such as hair liquids, hair mousses, hair rinses, hair conditioners, pomades, and hair glowen; liquid or powdery anti-perspirant agents; baby powder; deodorant spray for body; foot spray; body cleaners for nursing; and wet tissues. For animals, it may be applied in animal care agents such as deodorants, shampoos or rinses. In addition, cloths to touch the skin, for example, underwears, shirts, socks, shoes, various sanitary goods, and bandages may be made to emit aroma when used by impregnating or smearing them with the sustained-release aromatic of the invention. In addition, as bacteria usually present on the skin are present on the clothes which are once worn the clothes may emit aroma in a non-wearing state after a detergent, rinse agent or finishing agent in which the sustained-release aromatic of the invention is blended is applied to them by impregnation or smearing.
Other applications of the sustained-release aromatic of the invention include such where it is added in drinks or foods containing yeast, which may then emit aroma in a fermentation step. Thus, it is possible to confirm a degree of fermentation and, further, to reduce a loss of aroma, compared to the case where an aromatic is added before fermentation.
The sustained-release aromatic of the invention may also be used as a detecting indicator for confirming the presence of micro-organisms such as bacteria usually present on the skin and yeast, taking advantage of release of the perfume component with micro-organisms.
In the sustained-release aromatic of the invention, conventional materials may be added in addition to the aforesaid perfume derivatives, such as natural oils such as peppermint oil, spearmint oil, rose oil, patchouli oil, orange oil, neroli oil, and lemon oil; terpene type hydrocarbons such as xcex1-pinene, xcex2-pinene, terpinolene, and p-cymene; aliphatic alcohols such as cis-3-hexenol, n-undecylenic alcohol, and n-octhyl alcohol; terpene type alcohols such as linalool, geraniol, citroneliol, 1-menthol, nerolidol, and santalol; aromatic alcohols or derivatives thereof such as phenylethyl alcohol, cinnamic alcohol, methylphenyl carbinol, and t-buthyl cyclohexanol; phenols or derivatives thereof such as anisole, anethole, and eugenol; aliphatic aldehydes such as n-heptyl aldehyde, undecylenic aldehyde, and 2,6-nonadienal; terpene type aldehydes such as citral, citronellal, hydroxy citronellal, and perillaldehyde; aromatic aldehydes such as benzaldehyde, phenylacetaldehyde, cinnamic aldehyde, anisaldehyde, cuminaldehyde, heliotropine, cyclamenaldehyde, and vanillin; aliphatic ketones such as methyl n-amyl ketone, methyl heptenone, and diacetyl; terpene type cyclic ketones such as 1-carvone, menthone, piperitone, and camphor; cyclic ketones such as benzophenone, ionone, methylionone, irone, maltol, and jasmone; musk type perfume compounds such as large cyclic musks, e.g. muscone, cyclopentadecanone, and ethylene brassylate, nitro musk, and indan musk; oxides such as rose oxide, and linalool oxide; esters of aliphatic or aromatic acids and alcohols such as terpene alcohols, aliphatic alcohols, aromatic alcohols or phenols; nitrogen-containing perfume compounds; sulfur-containing perfume compounds; and blended perfumes in which two or more of these exemplified natural oils or perfume compounds are mixed.
In addition to the aforesaid compounds, the following materials may be added in the sustained-release aromatic of the invention: anti-perspirant agents such as aluminum chlorohydroxide(ACH); disinfectants such as 3,4,4xe2x80x2-trichlorocarbanilide (TCC); deodorants such as lauryl methacrylate, geranyl crotonate and flavonoid; pigments; and any other materials.
It is possible to add other types of perfumes than the perfume components of the perfume derivatives to the sustained-release aromatic of the invention in addition to the aforesaid perfume derivatives to vary aroma between a time before or just after the application and a time when the aromatic is being used. Thus, a change in aroma with the passage of time may be attained.